Liquid detergent composition

ABSTRACT

LIQUID DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF ONE OR MORE SOAPS OF FATTY ACIDS HAVING FROM 8 TO 22 CARBON ATOMS, THE CATIONS OF SAID FATTY ACID SOAPS BEING POTASSIUM AND AA CATION SELECTED FROM THE CLASS COMPRISING SODIUM, ETHANOLAMINE AND MIXTURES THEREOF, A SOLVENT COMPRISING WATER AND A HYDROTROPIC SUBSTANCE SELECTED FROM THE CLASS COMPRISING LOWER SATURATED MONOHYDRIC ALCOHOL HAVING 1 TO 4 CARBON ATOMS, POTASSIUM PARATOLUENESULPHONATE AND MIXTURES THEREOF. AND WETTING OR FLUIDIFYING AGENT SELECTED FROM THE CLASS COMPRISING GLYCEROL, ETHYLENE GLYCOL AND POLYETHYLENE GYLCOL WITH A MOLECULAR WEIGHT FROM 200 TO 600. THE LIQUID DETERGENT COMPOSITION CONTAINS ALSO SEQUESTERING AGENTS, EMULSIFYING AGENTS AND DEFOAMING AGENTS, AND INORGANIC AND ORGANIC SALTS.

United States Patent 3,723,328 LIQUID DETERGENT COMPOSITION CarloPelizza, Via Aurelia 38, Nervi, Italy No Drawing. Continuation-impart ofabandoned applications Ser. No. 500,320, Oct. 21, 1965, Ser. No.595,616, Nov. 21, 1966, Ser. No. 643,414, June 5, 1967, and Ser. No.774,188, Nov. 11, 1968. This application May 3, 1971, Ser. No. 139,926

Int. Cl. Clld 9/30, 3/066 US. Cl. 252-111 5 Claims ABSTRACT OF THEDISCLOSURE Liquid detergent composition consisting essentially of one ormore soaps of fatty acids having from 8 to 22 carbon atoms, the cationsof said fatty acid soaps being potassium and a cation selected from theclass comprising sodium, ethanolamine and mixtures thereof, a solventcomprising water and a hydrotropic substance selected from the classcomprising lower saturated monohydric alcohol having 1 to 4 carbonatoms, potassium paratoluenesulphonate and mixtures thereof, and wettingor fiuidifying agent selected from the class comprising glycerol,ethylene glycol and polyethylene glycol with a molecular weight from 200to 600. The liquid detergent composition contains also sequesteringagents, emulsifying agents and defoaming agents, and inorganic andorganic salts.

CROSS-REFERENCES TO RELATED APPLICATIONS This is a continuation-in-partapplication of the following applications: Ser. No. 500,320 filed onOct. 21, 1965, now abandoned, Ser. No. 595,616 filed on Nov. 21, 1966,now abandoned, Ser. No. 643,414 filed on June 5, 1967, now abandoned,Ser. No. 774,188 filed on Nov. 11, 1968, now abandoned.

BACKGROUND OF THE INVENTION In my copending application Ser. No.774,188, filed Nov. 11, 1968 I have disclosed a liquid detergentcomposition consisting essentially of:

(a) From 25 to 54%, by weight of the composition, of soap of fatty acidsselected from the group consisting of saturated fatty acids having from8 to 22 carbon atoms, unsaturated fatty acids having from 14 to 22carbon atoms and mixtures thereof, said soap of fatty acids beingselected from the group consisting of potassium soap, sodiumsoap,'ethanolamine soap and mixtures thereof, said potassium soap beingpresent in a quantity from 50 to 100% by weight of said soap of fattyacids, said sodium soap being present in a quantity up to 30% by weightof said soap of fatty acids and said ethanolarnine soap being present ina quantity up to 50% by weight of said soap of fatty acids;

(b) From 28 to 60%, by Weight of the composition, of a solventconsisting of water and a hydrotropic substance selected from the groupconsisting of lower saturated monohydric alcohol having from 1 to 4carbon atoms, potassium para toluenesulphonate and mixtures thereof; theratio by weight of said hydrotropic substance to Water being from 1:30to 3:1; and

(c) From 1 to 15%, by weight of the composition, of a fiuidifying agentselected from the group consisting of glycerol, ethylene glycol,polyethylene glycol having a molecular weight from 200 to 600 andmixtures thereof.

I have disclosed in my above said copending application 53 examples and18 tests of my above defined liquid detergent composition.

It is known that addition of salts in liquid detergent compositions ofthe above described kind improves the quality and properties of thecomposition. However, here- 3,723,328 Patented Mar. 27, 1973 tofore theadverse effect of salts within such a compositron was the increase inthe viscosity thereof, so that it was deemed to be not convenientheretofore to add salts beyond certain percentages, even if otherwise agreater quantity of salts could favourably influence the quality and theproperties of the composition.

SUMMARY OF THE INVENTION An object of the invention is to provide apotassium soap based liquid detergent composition including at least twoselected salt components which will diminish thi: increase in theviscosity thereof due to addition of sa ts.

Another object is to provide a potassium soap based liquid detergentcomposition including at least two selected salts, in which the selectedsalt components will display buffer and fluidifying actions on theliquid detergent composition allowing thereby to adjust the pH valuethereof to the desired use of the liquid detergent compositron.

Another object is to provide a potassium soap based liquid detergentcomposition including at least two selected salts, in which the selectedsalts will perform a synergetic action with each other and with theother components of the composition.

Another object is to provide a potassium soap based homogeneous liquiddetergent composition including at least two selected salts, which willbe limpid, will have a good fluidity and in which no separation ofphases will occur not even at near to 0 C. temperatures, and in whichthere is a stable equilibrium among the components thereof.

Another object is to provide a liquid detergent composition which willbe technically and economically satisfactory both for manual use and usein washing machines of industrial and household kind.

Another object is to provide a liquid detergent composition in which thephosphate components may easily be replaced by non-phosphate componentsin order to avoid the eutrophication phenomenon in waters.

Another object is to provide a liquid detergent composition having adegree of biodegradability higher than within 24 hours.

Another object is to provide a liquid detergent composition, which isnot toxic for surface water fauna under standardized test conditions.

A further object is to provide a liquid detergent composition which willreduce to a minimum the wear action under standardized test conditionwashing cycles.

Another object is to provide a liquid detergent composition which willattain, in addition to the above specified objects, also all otherobjects recited in my above specified copending and parent applications.

I have found that the following liquid detergent composition hereinafterindicated as incomplete LDC-A attains the above objects, when integratedwith selected salts of the kind specified hereinafter. The formulationof this incomplete LDC is as follows:

Percent by weight Potassium soap of fatty acids derived from olive oil13.25 Potassium soap of fatty acids derived from coconut oil 13.25

Water 43.30 Ethyl alcohol 6.83 Ethylene glycol 5.56 Nonyl phenoloxyethylated with 9 moles of ethylene oxide 3.18 Tetrapotassium salt ofethylene diamine tetraacetic acid 3.87

Percent by weight Optical bleach (Photine) 0.25 Defoaming agent:

Nonyl phenol oxyethylated with 1.5 moles of ethylene oxide 0.50 tributylphosphate 0.50 Citronella oil 0.10

I have found that the viscosity of this LDC-A is remarkably influenced,in a surprising manner, by the presence or absence of potassiumtetraborate and/or sodium tripolyphosphate.

Expectably, when only potassium tetraborate or only sodiumtripolyphosphate were singularly added to the above LDC the viscosity ofit increased remarkably.

In fact, from the prior art (e.g. Soap Manufacture, vol. I, by J.Davidsohn et al., 1953, p. 461) it is known that liquid detergentcompositions including fatty acid soaps in a hydroalcoholic solvent arethickened when inorganic salts are added thereto.

It was therefore surprising that, when both potassium tetraborate andsodium polyphosphate are added to the above LDC, the increase inviscosity unexpectedly diminished, even in cases where the total amountof these salts was greater than the singularly added salt.

On the basis of the tests and experiments carried out it seems to mereasonable to believe that this surprising behavior of the viscosity isdue to a synergetic action not only between the two mentioned saltsinvolved, but between all other main components of the LDC-A. In fact,the tests carried out and partly reported also in my above saidcopending application, showed the existence of a remarkably stableequilibrium between the compo nents of the LDC-A including the abovementioned salts, and a resistance to separation of the components evenat near to C. temperatures.

I have also found that the following inorganic salts alone or inadmixture with one another and/or with tetraborate sodiumtripolyphosphate display a similar synergetic action with the componentsof the above in- These examples illustrate the variation of viscosity inEngler degrees, of compositions in which various percentages ofpotassium tetraborate and sodium tripolyphosphate are added to theincomplete LDC-A specified in the summary of the invention.

Percent Sodium Potassium tripoly- E. at E. at E. at E. at Examplestetraborate phosphate C 23 C. 12 C. 24 C From the above examples itappears that when only sodium tripolyphosphate or only potassiumtetraborate are added, increasing amounts of these salts singularlyused, cause the viscosity with respect to that of the incomplete LDC-A,to increase at a higher rate than when these salts are used together,which is a surprising behaviour.

For example the viscosity of 23.23 E. of Example 5 surprisinglydiminishes to l9.63 E. of Example 8 when, in addition to 3.10% by weightof potassium tetraborate 6.31 weight percent of sodium tripolyphosphateare used, i.e. even if the total amount of these salts is far greaterthan in Example 5. In fact, one would normally expect the viscosity toincrease under these conditions, but exactly the opposite occurs in thisinvention.

This surprising effect may be construed as a showing of a synergeticaction not only between the two salts involved but also between thesesalts and the other components of the composition.

The following examples show that a similar effect may be obtained when,in addition to potassium tetraborate other inorganic or also determinedorganic salts are added to this or a similar composition.

EXAMPLES 9-23 These examples illustrate the viscosity in Engler degreesat 17.5 C. of compositions in which the indicated percentages ofpotassium tetraborate and one or more of other inorganic and organicsalts are added to an incomplete LDC-B. The incomplete LDC-B is equal toincomplete LDC-A except for the defoaming agent mixture in which theratio between nonyl phenol oxyethylated with 1.5 moles of ethylene oxideand tributyl phosphate is 1:3 instead of 1:1, the total amount ofdefoaming mixture remaining substantially the same.

Potassium tetra- Other salts borate, weight Weight E. at Examplespercent Kind percent 17.5 C.

0 0 18. 84 3.1 0 25.12 3.1 Sodium tripolyphosphate- 6. 31 19. 20 3.1Sodium carbonate 6. 31 16 3. 1 Potassium carbonate 6.31 12.12 3.1Tetrapotassium pyrophos- 6. 31 16. 30

phate 3 H2O. 3.1 Tetrasodium pyrophos- 6. 31 19.10

phate 10 0. 3.1 Trfisolium phosphate 12 6. 31 22. 84

2 3.1 Tripotassium phosphate. 6. 31 15. 30 3.1 Sodium bicarbonate... 6.31 18.00 3. 1 Potassium bicarbonate 6.31 16. 04 3.1 Sodiumnitriltriacetate.. 6. 31 18. 00 3. 1 Potassium nitriltriacetate. 6. 3117. 00 3.1 Sodium metasilicate 5 H2O 18.00

Sodium metasilicate 5 H2O" 3.15 3.1 plus 17. 00

Sodium tripolyphosphate. 3.15

I have also found that when one or more of the salts of Examples 923 areadded to LDC-B so that the total amount of the mixture of these salts isabout 6.31 weight percent with respect to the total composition similarresults in viscosity are obtained.

I have also found that, when as emulsifying agent an alkylphenoloxyethylated with 5-6 moles of ethylene oxide and oleic alcoholoxyethylated with 5-6 moles of ethylene are used, similar satisfactoryresults are obtained.

It seems to me reasonable to believe that also the liquid detergentcompositions described in the 53 examples of my above said copendingapplication would behave in a similar manner when salts of the abovedescribed kind are added therein.

The compositions of Examples 8 and 11 were subjected to the 18 testsdescribed in my above said copending application and similar resultshave been obtained.

In addition to the above tests the composition of Example 8 has beensubjected to the following toxicological analysis:

Toxicological Analysis This analysis has been carried out according toconventional methodology using goldfish exemplars (Carassius auratus L.)in groups of 6 exemplars for each dilution of Observation at 24 hoursConcentration (g./l.) 6 hours 48 hours 72 hours 0. ..do 2dead 4alive..-4alive. 0. do. 6alive 6a1ive fialive. 0. do 2dead 4 alive 4 alive. 0. do6 alive 6 alive.-. 6 alive. 0. do "do o Do. 0. .do.. do. do Do. 0. do do.do Do.

From the above description and from the disclosure of my above specifiedcopending application it appears that the described liquid detergentcompositions attain all the objects set out in the summary of theinvention.

It appears further that the potassium tetraborate is present in thecomposition in the amount of about 30% by weight with respect to thetotal amount of the inorganic salts.

It appears further that, in cooperation with the other mentionedinorganic salts, and with sodium and potassium nitrilotriacetate,potassium tetraborate has a buffering action on pH and a fluidifyingaction on the liquid composition.

-It appears further that the total amount of inorganic salts containedin the composition in admixture with potassium tetraborate is about 33%by weight with respect to the potassium salt.

It appears further that the concentration of the inorganic salts in theexisting water is of about 20% by weight.

It appears further that the concentration of inorganic salts in admixingwith sodium and potassium nitriloacetate, in the existing water is ofabout 20%.

It appears further that the ratio between potassium borate and theinorganic salts is about 1:2.

It appears further that the ratio between potassium borate and sodiumand potassium nitriltriacetate is about 1:2.

It appears further that the ratio between the potassium borate and themixtures of inorganic salts and sodium and potassium nitriltriacetate isabout 1:2.

It appears further that the potassium soap component of the compositionis constituted of 50% by weight of potassium soap of fatty acids derivedfrom olive and 50% by weight of potassium soap of fatty acids derivedfrom coconut oil.

It appears further that all the components of the liquid detergentcomposition of this invention display a synergetic action among eachother.

What is claimed is:

1. A liquid detergent composition consisting essentially of:

(a) from 25% to 35% by weight of the composition of potassium soap offatty acid comprising, by weight, from zero up to 3% saturated fattyacid (C -C from zero up to 10% saturated fatty acid (C from zero up to30% unsaturated linoleic acid (C from zero up to 50% unsaturatedricinoleic acid (C from 20% to 100% unsaturated oleic acid (C from zeroup to 10% unsaturated myristic acid 5 (C from zero up to 30% unsaturatedlauric acid (C and from zero up to 5% of colophony,

(b) from 28% to 55% by weight of the composition of a solvent consistingof Water and a hydrotropic substance selected from the group consistingof lower saturated monohydric alcohol having from 1 to 4 carbon atoms,potassium para-toluenesulphonate and mixtures thereof, the ratio byweight of hydrotropic substance to water being from 123-0 to 3: 1,

(c) from 1 to 15% by weight of the composition, of a 1 fluidifying agentselected from the group consisting of glycerol, ethylene glycol,polyethylene glycol having a molecular Weight (M.W.) from 200 to 600 andmixtures thereof,

(d) from 1% to 25 by weight of the composition, of an organic dispersingagent selected from the group consisting of alkali metal sulphoricinate,octyl and nonyl phenol ester oxyethylated with from 7 to 12 moles ofethylene oxide, polyethylene glycol monooleate having a MJW. from 200 to600, higher fatty alcohols having from 12 to 18 carbon atoms andoxyethylated with from 16 to 25 moles of ethylene oxide, sulphatedhigher fatty alcohols,

(e) from 1% to 25% by weight of the composition, of an organicsequestering agent selected from the group consisting of salts ofethylene diamine tetraacetic acid, potassium gluconate and mixturesthereof,

(f) from 1 to 10% by weight of the composition, of an emulsifying agentselected from the group consisting of monoethanolamine, diethanolamine,triethanolamine alkyl phenols and oleic alcohols both oxyethylated with5-6 moles of ethylene oxyde and mixtures thereof,

(g) from 1% to 7% by weight of the composition, of

potassium tetraborate,

(h) from 3% to 30% by Weight of the composition, of inorganic saltselected from the group consisting of potassium carbonate, sodiumcarbonate, potassium dibasic phosphate, sodium dibasic phosphate,potassium tribasic phosphate, sodium tribasic phosphate, potassiumtetrabasic pyrophosphate, sodium tetrabasic pyrophosphate, potassiumtripolyphosphate, sodium tripolyphosphate and mixtures thereof.

2.. A liquid detergent composition consisting essentially of:

13.25 potassium soap of fatty acids derived from olive oil;

13.25% potassium soap of fatty acids derived from 55 coconut oil;

43.30% of water, 683% of ethyl alcohol, 5.56% of ethylene glycol, 3.18%of nonyl phenol oxyethylatecl with 9 moles of ethylene oxide;

3.87% tetrapotassium salt of ethylene diamine tetraacetic acid, 0.25%optical bleach, 0.25% of nonyl phenol oxyethylated with 1.5 moles ofethylene oxide, 0.75% of tributyl phosphate, 0.1% of citronella oil,3.10% potassium tetraborate, 6.31% of sodium tripolyphosphate, allpercentages being by weight.

65 3. A composition according to claim 2, wherein at least a part ofsodium tripolyphosphate is replaced by at least one inorganic saltselected from the group consisting of sodium carbonate, potassiumcarbonate, tetrapotassium pyrophosphate.3H O, tetrasodium pyrophosphate10H O, trisodium phosphate and mixtures thereof.

4. A composition according to claim 2, wherein at least a part of sodiumtripolyphosphate is replaced by at least one inorganic salt selectedfrom the group consisting of tripotassium phosphate, sodium bicarbonate,potassium bicarbonate, sodium metasiIicateSH O and mixtures thereof.

5. A composition according to claim 2, wherein at least a part of sodiumtripolyphosphate is replaced by at least one organic salt selected fromthe group consisting of potassium nitrile triacetate, sodium nitriletriacetate and mixtures thereof.

References Cited UNITED STATES PATENTS OTHER REFERENCES TergitolSurfactants, Union Carbide Co., 1961, pp. 4, 8 and 29.

Surfonic Technical Bulletin, Jefferson Chemical Co.,

JOHN D. WELSH, Primary Examiner US. Cl. X.R. 252527

